US2591877A - Purification of alcohols by azeotropic distillation - Google Patents
Purification of alcohols by azeotropic distillation Download PDFInfo
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- US2591877A US2591877A US50446A US5044648A US2591877A US 2591877 A US2591877 A US 2591877A US 50446 A US50446 A US 50446A US 5044648 A US5044648 A US 5044648A US 2591877 A US2591877 A US 2591877A
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- alcohols
- methyl
- cyclohexane
- mixture
- butanol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
- C07C29/82—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by azeotropic distillation
Definitions
- This invention relates :to the production of purified organic compounds, and relates more particularly to the separation and purification of certain mixture of organic compoundsobtained when isolating the products of the vapor phase partial oxidation, with air or oxygen, of gaseous hydrocarbons, such as propane, butane, or mixtures thereof.
- gaseous hydrocarbons such as propane, butane, or mixtures thereof.
- An object of this invention is the provision of an eflicient and economical process for the separation of purifiedn-propanol, isobutanol and nbutanol from a crude fraction containing a mixture of said compounds together with various acetals, carbonyl compounds and oxides as impurities.
- the purifica-- tion involves a series of fractional distillation operations yielding a number of crude fractions each containing a plurality of compounds.
- One such fraction which is obtained during the process comprises a mixture of n-propanol, isobutanol, secondary butanol, and 'n-butanol containing various acetals, esters, carbonyl compounds and oxides.
- the separation of the alcohols from the other components is complicated by the fact that they all have boiling points which are relatively close to one another and a straight fractional distillation does not effect a satisfactory separation.
- the alcohols present in a mixture comprising n-propanol, isobutanol, secondary butanol, n-butanol, esters, acetals, carbonyl compounds and oxides may be separated from the other components in an eflicient and economical manner if said mixture is fractionated to separate a crude fraction therefrom containing the alcohols normally boiling below about 100 C. and a crude fraction containing and each fraction then subjected to an azeotropic distillation employing as the entraining agent an alkyl-cyclohexane, such as methyl-cyclohexane. The azeotropic distillates obtained each com.-
- the initial fractionation of the crude mixture is so effected that the fractions separated comprise one boiling at from about 96 to 103 C. and the other at from about 103 to C.
- the alcohols in the methyl-cyclohexane-alcohol azeotropes obtained maybe separated by combining the azeotropes and subjecting the combined azeotropes to a further distillation in a methyl-cyclohexane recovery column employing methanol as the entraining agent.
- the methanol removes the methyl-cyclohexane as a methyl cyclohexane-menthanol azeotrope and the mixture of alcohols which remains may then be separated by ordinaryfractionation methods into the individual alcohols present therein.
- the alcohols in the methyl-cyclohexane-alcohol azeotropes may be recovered by distilling the azeotropes separately rather than combining them.
- the methyl-cyclohexane-menthanol azeotrope may be separated and the methyl-cyclohexane and methanol recycled in the process by extracting the methyl-cyclohexane-methanol azeotrope with water.
- the methyl-cyclohexane separates in the extractor as a water-immiscible layer and is recycled to effect a further separation of alcohols from the acetal, carbonyl and oxide impurities. water extract by distillation and the water is recycled to the water extractor.
- the methanol thus separated is recycled to the methyl-cyclohexane recovery column where the methyl-cyclohexane is recovered as the methyl-cyclohexanemethanol azeotrope previously mentioned, and a mixture of n-propanol, isobutanol, secondary butanol and n-butanol is recovered as the residue from the reboiler of said methyl-cyclohexane recovery column.
- Fractional distillation of this latter mixture of alcohols allows the separation of n-propanol and secondary butanol as the initial distillate and the mixture of isobutanol and n-butanol remaining is then separated by a second fractionation, the isobutanol comprising The methanol is stripped from the the distillate and the n-butanol the column residue.
- Our novel method of separating the undesirable impurities from the crude fraction of alcohols employing an alkyl'cyclohexane, such as methyl-cyclohexane, as the entraining agent may thus be carried out in :a continuous .fashion and offers an efiicient and economical means for the purification of said alcohols and the removal therefrom of contaminants.
- acetals, carbonyl compounds and'oxides as impurities whereby said impurities are removed, which comprises fractionating the mixture to separate from the same a crude fraction boiling at from 96 to 103 C. and a crude fraction boiling at from about 103 to 120 C., subjecting each of said fractions to azeotropic distillation employing methylcyclohexane gas the alcohol entraining agent, combining the azeotropic distillates and separating said alcohols from the combined azeotropic 'distillates by "azeo'troping said distillates with methanol whereby the methyl-cyclohexane is separated therefrom as a methyl-cyclohexanemethanol azeotrope.
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Apr. 8, 1952 i UNITED STATE PURIFICATION OF ALCOHOLSBY AZEOTROPIC DISTILLATION Nat C. Robertson, and RobertH; Buchanan, Corpus Christi, Tex., assignors to Celanese Corporation of America, a corporation of Delaware No Drawing. Application September21, 1948,
SerialNo. 50,446
1 This invention relates :to the production of purified organic compounds, and relates more particularly to the separation and purification of certain mixture of organic compoundsobtained when isolating the products of the vapor phase partial oxidation, with air or oxygen, of gaseous hydrocarbons, such as propane, butane, or mixtures thereof. r I
An object of this invention is the provision of an eflicient and economical process for the separation of purifiedn-propanol, isobutanol and nbutanol from a crude fraction containing a mixture of said compounds together with various acetals, carbonyl compounds and oxides as impurities.
Other objects of this invention will appear from the following detailed description.
The vapor phase, partial oxidation of aliphatic hydrocarbons such as propane or butane, or mixtures thereof, employing air or oxygen as the oxidizing agent, yields a complex mixture of products including formaldehyde, acetaldehyde, methanol, propionaldehyde, allyl alcohol, n-propanol, isobutanol, secondary butanol, n-butanol, acetone, methyl ethyl ketone, methylal, acrolein, tetrahydrofuran, methyl formate and other esters, formals, acetals and various oxides, as
3 Claims. (01. 202-42) the alcohols normally boiling above about 166 C.,
well as numerous other aliphatic compounds in varying amounts. In order to separate the complex mixture of oxidation products and to purify each of the components so that the same will be suitable for commercial use, an intricate product purification scheme is necessary. The purifica-- tion involves a series of fractional distillation operations yielding a number of crude fractions each containing a plurality of compounds. One such fraction which is obtained during the process comprises a mixture of n-propanol, isobutanol, secondary butanol, and 'n-butanol containing various acetals, esters, carbonyl compounds and oxides. The separation of the alcohols from the other components is complicated by the fact that they all have boiling points which are relatively close to one another and a straight fractional distillation does not effect a satisfactory separation.
We have now found that the alcohols present in a mixture comprising n-propanol, isobutanol, secondary butanol, n-butanol, esters, acetals, carbonyl compounds and oxides may be separated from the other components in an eflicient and economical manner if said mixture is fractionated to separate a crude fraction therefrom containing the alcohols normally boiling below about 100 C. and a crude fraction containing and each fraction then subjected to an azeotropic distillation employing as the entraining agent an alkyl-cyclohexane, such as methyl-cyclohexane. The azeotropic distillates obtained each com.-
prise a mixture of methyl-cyclohexane and the.
alcohols originally present in each of said crude fractions while the residue which is drawn from the reboiler of the fractionating towers in which the azeotropic distillations take place comprises the esters, acetals, carbonyl compounds and oxides originally present in the starting mixture.- Preferably, the initial fractionation of the crude mixture is so effected that the fractions separated comprise one boiling at from about 96 to 103 C. and the other at from about 103 to C.
The alcohols in the methyl-cyclohexane-alcohol azeotropes obtained maybe separated by combining the azeotropes and subjecting the combined azeotropes to a further distillation in a methyl-cyclohexane recovery column employing methanol as the entraining agent. The methanol removes the methyl-cyclohexane as a methyl cyclohexane-menthanol azeotrope and the mixture of alcohols which remains may then be separated by ordinaryfractionation methods into the individual alcohols present therein. If desired, the alcohols in the methyl-cyclohexane-alcohol azeotropes may be recovered by distilling the azeotropes separately rather than combining them.
The methyl-cyclohexane-menthanol azeotrope may be separated and the methyl-cyclohexane and methanol recycled in the process by extracting the methyl-cyclohexane-methanol azeotrope with water. The methyl-cyclohexane separates in the extractor as a water-immiscible layer and is recycled to effect a further separation of alcohols from the acetal, carbonyl and oxide impurities. water extract by distillation and the water is recycled to the water extractor. The methanol thus separated is recycled to the methyl-cyclohexane recovery column where the methyl-cyclohexane is recovered as the methyl-cyclohexanemethanol azeotrope previously mentioned, and a mixture of n-propanol, isobutanol, secondary butanol and n-butanol is recovered as the residue from the reboiler of said methyl-cyclohexane recovery column. Fractional distillation of this latter mixture of alcohols allows the separation of n-propanol and secondary butanol as the initial distillate and the mixture of isobutanol and n-butanol remaining is then separated by a second fractionation, the isobutanol comprising The methanol is stripped from the the distillate and the n-butanol the column residue.
Our novel method of separating the undesirable impurities from the crude fraction of alcohols employing an alkyl'cyclohexane, such as methyl-cyclohexane, as the entraining agentmay thus be carried out in :a continuous .fashion and offers an efiicient and economical means for the purification of said alcohols and the removal therefrom of contaminants.
It is to be understood that the foregoing detailed description is given merely by way'o'f illustration and that many variations may be made therein without departing from thespirit of 10111 invention.
Having described our invention, what we desire to secure by Letters Patent is:
1. In a process for the removal of acetals, ca rbonyl compounds and oxides from a mixture comprising essentially n-propanol, isobutanol, secondary ibuta'nol and n-butanol wherein said esters, :acetals, carbonyl compounds, and oxides are present as impurities, the step which oompr ises fractionating'the mixture to separate from the same :a crude fraction boiling at from about 96 to "1 03 C. and a crude fraction boiling at from about 103 to r20 C. "and then subjecting each of said fractions to azeotropic distillation employ-ing =methyl-cyclohexane as the alcohol entrain'ing agent, whereby the said alcohols are removed from :said fractions.
Process for the treatment of a mixture toomprising essentially n-propano'l, isobutanol, secondary butanol and 'n-butanol containing esters, acetals, carbonyl compounds and oxides as impurities whereby said impurities are -removed, which comprises i-ractionating the mixture to separate from the same a crude fraction boiling at from about 96 to 103 -C. and a crude fraction boiling at from about 103 to 120 'C., subjecting each of said fractions to azeotropic distillation employing methyl-cyclohexane the alcohol entraining agent, and separating said alcohols from the azeo-tropic dist-illates obtained by'azeotroping 4 7 said distillates with methanol whereby the methyl-cyclohexane is separated therefrom as a methyl-cyclohexane-methanol azeotrope.
3. Process for the treatment of a mixture comprising essentially n-propanol, isobutanol, secondary butanol and n-butanol containing esters,
acetals, carbonyl compounds and'oxides as impurities whereby said impurities are removed, which comprises fractionating the mixture to separate from the same a crude fraction boiling at from 96 to 103 C. and a crude fraction boiling at from about 103 to 120 C., subjecting each of said fractions to azeotropic distillation employing methylcyclohexane gas the alcohol entraining agent, combining the azeotropic distillates and separating said alcohols from the combined azeotropic 'distillates by "azeo'troping said distillates with methanol whereby the methyl-cyclohexane is separated therefrom as a methyl-cyclohexanemethanol azeotrope.
NAT 0. ROBERTSON. ROBERT BUCHANAN REFERENCE-S CITE-15 I The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,341,433 Fisher Feb. 8, 194 4 2,351,527 Lambeolce June 113, 21.944 2376, 870 Engel May 29, 1945 2,386,058 Patterson et al. Oct. 2, 1945 2,476,205 'McCants July 12, lSlQ 2,476,206 McCant-s July 12, I949 o'rnaa REFERENCES
Claims (1)
1. IN A PROCESS FOR THE REMOVAL OF ACETALS, CARBONYL COMPOUNDS AND OXIDES FROM A MIXTURE COMPRISING ESSENTIALLY N-PROPANOL, ISOBUTANOL, SECONDARY BUTANOL AND N-BUTANOL WHEREIN SAID ESTERS, ACETALS, CARBONYL COMPOUNDS, AND OXIDES ARE PRESENTS AS IMPURITIES, THE STEPS WHICH COMPRISES FRACTIONATING THE MIXTURE TO SEPARATE FROM THE SAME A CRUDE FRACTION BOILING AT FROM ABOUT 96 TO 103* C. AND A CRUDE FRACTION BOILING AT FROM ABOUT 103 TO 120* C. AND THEN SUBJECTING EACH OF SAID FRACTIONS TO AZEOTRPIC DISTILLATION EMPOLYING METHYL-CYCLOHEXANE AS THE ALCOHOL ENTRAINING AGENT, WHEREBY THE SAID ALCOHOLS ARE REMOVED FROM SAID FRACTIONS.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US50446A US2591877A (en) | 1948-09-21 | 1948-09-21 | Purification of alcohols by azeotropic distillation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US50446A US2591877A (en) | 1948-09-21 | 1948-09-21 | Purification of alcohols by azeotropic distillation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2591877A true US2591877A (en) | 1952-04-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US50446A Expired - Lifetime US2591877A (en) | 1948-09-21 | 1948-09-21 | Purification of alcohols by azeotropic distillation |
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| US (1) | US2591877A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2666736A (en) * | 1950-06-09 | 1954-01-19 | Celanese Corp | Separation of n-propyl and sec. butyl alcohols by azeotropic distillation |
| US2875138A (en) * | 1955-01-17 | 1959-02-24 | Exxon Research Engineering Co | Purification of secondary butyl alcohol |
| US3431181A (en) * | 1966-06-22 | 1969-03-04 | Melle Bezons | Method of separating methanol from low boiling aliphatic esters and water by azeotropic distillation with a hydrocarbon |
| US4518462A (en) * | 1980-06-20 | 1985-05-21 | Asahi Kasei Kogyo Kabushiki Kaisha | Distillation process for purifying methyl methacrylate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2341433A (en) * | 1941-04-22 | 1944-02-08 | Eastman Kodak Co | Separation of solvents |
| US2351527A (en) * | 1941-04-22 | 1944-06-13 | Cities Service Oil Co | Refining low-boiling alcohols |
| US2376870A (en) * | 1941-03-28 | 1945-05-29 | Allied Chem & Dye Corp | Azeotropic distillation of hydro-carbon oils |
| US2386058A (en) * | 1941-08-01 | 1945-10-02 | Standard Oil Dev Co | Purification of organic liquids |
| US2476206A (en) * | 1945-08-04 | 1949-07-12 | Skelly Oil Co | Purification of methanol by azeotropic distillation |
| US2476205A (en) * | 1945-08-04 | 1949-07-12 | Skelly Oil Co | Refining of crude methanol by azeotropic distillation |
-
1948
- 1948-09-21 US US50446A patent/US2591877A/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2376870A (en) * | 1941-03-28 | 1945-05-29 | Allied Chem & Dye Corp | Azeotropic distillation of hydro-carbon oils |
| US2341433A (en) * | 1941-04-22 | 1944-02-08 | Eastman Kodak Co | Separation of solvents |
| US2351527A (en) * | 1941-04-22 | 1944-06-13 | Cities Service Oil Co | Refining low-boiling alcohols |
| US2386058A (en) * | 1941-08-01 | 1945-10-02 | Standard Oil Dev Co | Purification of organic liquids |
| US2476206A (en) * | 1945-08-04 | 1949-07-12 | Skelly Oil Co | Purification of methanol by azeotropic distillation |
| US2476205A (en) * | 1945-08-04 | 1949-07-12 | Skelly Oil Co | Refining of crude methanol by azeotropic distillation |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2666736A (en) * | 1950-06-09 | 1954-01-19 | Celanese Corp | Separation of n-propyl and sec. butyl alcohols by azeotropic distillation |
| US2875138A (en) * | 1955-01-17 | 1959-02-24 | Exxon Research Engineering Co | Purification of secondary butyl alcohol |
| US3431181A (en) * | 1966-06-22 | 1969-03-04 | Melle Bezons | Method of separating methanol from low boiling aliphatic esters and water by azeotropic distillation with a hydrocarbon |
| US4518462A (en) * | 1980-06-20 | 1985-05-21 | Asahi Kasei Kogyo Kabushiki Kaisha | Distillation process for purifying methyl methacrylate |
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